Chemiluminescence from alkyl hyponitrites in viscous liquid media

Abstract

We have studied the effect of dissolved polymers and mineral oil on the chemiluminescence from tert-butylbenzene solutions of trans -di-2-propylhyponitrite (IPHN), trans -di-1-phenylethyl hyponitrite (PEHN) and 3,3,4,4-tetramethyl-1,2-dioxetane (TMD) in the presence of a fluorescent species (2-tert-butyl-9,10-dibromoanthracene). It was found that the addition of polymers (poly(αmethylstyrene) and others) to solutions of the hyponitrites or TMD decreased their chemiluminescence. In contrast, addition of mineral oil decreased the luminescence from TMD but increased the luminescence from the hyponitrites. The decrease in luminescence was ascribed to the expected reduced rates of energy transfer to the fluorescent species in competition with decay of the carbonyl triplets. The increase in luminescence on addition of mineral oil was too be larger cage effects in the case of PEHN. The increase was tentatively ascribed to higher excited state formation efficiencies from alkoxyl radical dismutation in more viscous media.